CN114073922A - Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof - Google Patents
Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof Download PDFInfo
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- CN114073922A CN114073922A CN202010842788.6A CN202010842788A CN114073922A CN 114073922 A CN114073922 A CN 114073922A CN 202010842788 A CN202010842788 A CN 202010842788A CN 114073922 A CN114073922 A CN 114073922A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 70
- 239000002077 nanosphere Substances 0.000 title claims abstract description 66
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims abstract description 63
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 238000003384 imaging method Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 56
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 38
- 239000005711 Benzoic acid Substances 0.000 claims description 19
- 235000010233 benzoic acid Nutrition 0.000 claims description 19
- RSKDYRKXGSFNKK-UHFFFAOYSA-N C(=O)(O)C1=CC=C(C=C1)[Zn] Chemical compound C(=O)(O)C1=CC=C(C=C1)[Zn] RSKDYRKXGSFNKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YCACADGRMVEVPP-UHFFFAOYSA-N OC(=O)C1=CC=C([Mn])C=C1 Chemical compound OC(=O)C1=CC=C([Mn])C=C1 YCACADGRMVEVPP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- DTKKSWSQNRKYOS-UHFFFAOYSA-N C(=O)(O)C1=CC=C(C=C1)[Co] Chemical compound C(=O)(O)C1=CC=C(C=C1)[Co] DTKKSWSQNRKYOS-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 206010028980 Neoplasm Diseases 0.000 abstract description 3
- 201000011510 cancer Diseases 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910000896 Manganin Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- YMIJUYZSODEEOV-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Fe] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Fe] YMIJUYZSODEEOV-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/025—Applications of microcapsules not provided for in other subclasses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Polymers & Plastics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a porphyrin-based metal-organic framework nanosphere as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerant, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure micron sheet; and adding polyethyleneimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres. The method comprises the steps of obtaining a thin yarn-shaped micron large-size sheet by adjusting the proportion of porphin to metal ions, and then further reacting to obtain a porphyrin-based metal-organic framework nanosphere with uniform-scale micropores and mesopores coexisting; meanwhile, the porphyrin-based metal-organic framework nanosphere prepared by the method has wide application prospects in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework nano materials, and particularly relates to a porphyrin-based metal-organic framework nanosphere, a preparation method and application thereof, and in particular relates to a porphyrin-based metal-organic framework nanosphere which is constructed by gauze-shaped micrometer sheets in a polyethyleneimine condensation mode and has micropores and mesopores coexisting, and a preparation method and application thereof.
Background
The large specific surface area and ordered pore structure of the metal-organic framework material endow the metal-organic framework material with various applications in gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like. Although metal-organic framework materials are largely prepared and studied, few metal-organic framework micron sheets with the size of 1-20 μm are synthesized in a gauze shape, and further, no mention is made of the fact that the gauze-shaped metal-organic framework sheets with the micron size are condensed into nano spheres with micropores and mesopores coexisting. The nanosphere obtained by condensing the gauze-shaped sheet metal-organic framework has a structure with coexisting micropores and mesopores, can effectively load one or more substances such as micromolecules, macromolecules, proteins, nano large particles and the like, and has a wider application prospect, so that the development of a simple and effective method for synthesizing the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores has important significance.
Disclosure of Invention
The invention mainly aims to provide a porphyrin-based metal-organic framework nanosphere as well as a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a porphyrin-based metal-organic framework nanosphere, which comprises the following steps:
reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerant, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure micron sheet;
and adding polyethyleneimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres.
The embodiment of the invention also provides the porphyrin-based metal-organic framework nanosphere prepared by the method, the porphyrin-based metal-organic framework nanosphere has a micropore and mesoporous structure, and the diameter of the porphyrin-based metal-organic framework nanosphere is 50-200 nm.
The embodiment of the invention also provides application of the porphyrin-based metal-organic framework nanosphere in the fields of gas storage and separation, fuel cell performance conversion or biomedical imaging.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method utilizes the characteristic that meso-tetra (4-carboxyphenyl) porphin or porphin and metal ions thereof are coordinated under a certain condition, obtains a two-dimensional metal-organic framework structure micron sheet with a micron size like a gauze by adjusting the proportion and carrying out oil bath heating, and then adds polyethyleneimine to carry out controllable condensation to obtain the porphyrin-based metal-organic framework nanospheres with uniform particle size and coexisting micropores and mesopores, and has the advantages of simple operation, easy implementation and no need of assistance of expensive instruments;
(2) the invention firstly utilizes the gauze-shaped micron-sized metal-organic framework sheet to condense into the porphyrin-based metal-organic framework nanospheres with the coexistence of micropores and mesopores, and meanwhile, the porphyrin-based metal-organic framework nanospheres prepared by the invention have larger specific surface area and pore structure, can effectively load one or more substances such as micromolecules, macromolecules, proteins, nano-macroparticles and the like, and have wide application prospect in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM photograph of a two-dimensional metal-organic framework-structured nanosheet in example 10 of the present invention;
FIG. 2 is a TEM photograph of a nanosphere of porphyrin-based metal-organic framework in example 10 of the present invention;
FIG. 3 is a nitrogen adsorption-desorption curve of the porphyrinoid-organic skeleton nanosphere in example 10 of the present invention;
fig. 4 is a pore size distribution curve of the porphyrinato-metal-organic framework nanosphere in example 10 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing a porphyrin-based metal-organic framework nanosphere, which comprises:
reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerant, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure micron sheet;
and adding polyethyleneimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres.
In some more specific embodiments, the metalloporphin includes any one or a combination of two or more of meso-tetra (4-carboxyphenyl) iron porphin, meso-tetra (4-carboxyphenyl) copper porphin, meso-tetra (4-carboxyphenyl) zinc porphin, meso-tetra (4-carboxyphenyl) cobalt porphin, meso-tetra (4-carboxyphenyl) manganese porphin, without being limited thereto.
Further, the metal ions include any one or a combination of two or more of copper ions, cobalt ions, and nickel ions, and preferably copper ions.
Further, the accelerator comprises any one or combination of more than two of benzoic acid, polyvinylpyrrolidone and biphenyl dicarboxylic acid, and benzoic acid is preferred.
In the invention, the benzoic acid is used for promoting the metal coordination of the porphyrin center to form metal porphyrin and reducing H-accumulation and J-aggregation between sheet layers, and the polyvinylpyrrolidone (PVP) and the biphenyldicarboxylic acid have the same effect.
In the present invention, the branched long-chain polymer can also exhibit the same effect as polyethyleneimine.
In some more specific embodiments, the preparation method specifically comprises: dissolving meso-tetra (4-carboxyphenyl) porphin and/or metalloporphin in an organic solvent to form a meso-tetra (4-carboxyphenyl) porphin solution and/or a metalloporphin solution, and mixing with the metal ions, the promoter, the organic solvent and water to form the mixed reaction system.
Further, the concentration of the meso-tetra (4-carboxyphenyl) porphin solution and/or the metalloporphin solution is 0.1-10.0 mmol/L.
In some more specific embodiments, the metal ion is derived from a salt solution containing the metal ion.
Further, the salt solution includes any one or a combination of two or more of nitrate, chloride, sulfate, acetate, and phosphate, and is not limited thereto.
Furthermore, the concentration of the metal ions in the salt solution containing the metal ions is 0.1-10.0 mmol/L.
Further, the concentration of the benzoic acid is 1.0-30.0 g/L.
In some more specific embodiments, the molar ratio of the meso-tetra (4-carboxyphenyl) porphin and/or the metalloporphin, the metal ion and the promoter is 1-10: 1-10.
Further, the organic solvent includes any one or a combination of two or more of N, N-dimethylformamide, dimethylsulfoxide, methanol, ethanol and chloroform, and is not limited thereto.
In some specific embodiments, the two-dimensional metal-organic framework structure micron sheet is a gauze-shaped two-dimensional metal-organic framework structure micron sheet, the size is 1-20 μm, and the thickness is 1-20 nm.
Furthermore, the molecular weight of the polyethyleneimine is 600-25000 g/mol.
Furthermore, the polyethyleneimine is derived from a polyethyleneimine solution with the concentration of 1-1000 mg/L.
The embodiment of the invention also provides porphyrin-based metal-organic framework nanospheres prepared by the method, wherein the porphyrin-based metal-organic framework nanospheres have a micropore and mesopore structure, the diameter of the porphyrin-based metal-organic framework nanospheres is 50-200 nm, and the specific surface area of the porphyrin-based metal-organic framework nanospheres is 500-1500 m2/g。
Furthermore, the pore size of the microporous structure of the porphyrin-based metal-organic framework nanosphere is 0.8-1.5 nm, and the pore size of the mesoporous structure of the porphyrin-based metal-organic framework nanosphere is 5-40 nm.
In some more specific embodiments, the method of making comprises:
(1) mixing meso-tetra (4-carboxyphenyl) porphine or its metal porphine, copper metal ions, benzoic acid, an organic solvent and water to form a solution;
(2) adjusting the molar ratio of porphine, copper metal ions and benzoic acid in the mixed solution, and reacting in an oil bath heating mode to obtain a two-dimensional metal-organic framework structure micron sheet with the size of 1-20 microns and the same shape as a gauze;
(3) and adding polyethyleneimine and the gauze-shaped micron sheet into the mixed solution, and condensing under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores.
In another aspect of the embodiments of the present invention, there is also provided a use of the aforementioned porphyrin-based metal-organic framework nanospheres in the fields of gas storage and separation, fuel cell performance conversion, and biomedical imaging.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Meso-tetra (4-carboxyphenyl) porphine used in this example was purchased from Tokyo chemical industries, Inc.; copper nitrate and N, N-dimethylformamide were purchased from the national pharmaceutical group.
Preparing 1.0mmol/L of meso-tetra (4-carboxyphenyl) porphine solution by taking N, N-dimethylformamide as a solvent, preparing 10.0mmol/L of copper nitrate solution by taking water as a solvent, adding 2mL of the meso-tetra (4-carboxyphenyl) porphine solution and 1mL of the copper nitrate solution into a 100mL round bottom flask, then adding 10mL of N, N-dimethylformamide and 0.05g of benzoic acid, uniformly stirring, carrying out oil bath heating reaction on the uniformly mixed solution under stirring at the temperature of 90 ℃ for 4 hours, and cooling to room temperature after the reaction is finished. And then, adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5h at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with the coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 60 nm.
Example 2
In this example, N-dimethylformamide is used as a solvent to prepare a 0.1mmol/L solution of meso-tetra (4-carboxyphenyl) porphin, and then water is used as a solvent to prepare a 0.1mmol/L solution of copper chloride. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of copper chloride solution were added to a 100mL round-bottomed flask, 10mL of N, N-dimethylformamide was added, 0.05g of benzoic acid was added, and the mixture was stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 50 ℃, the reaction time is 5h, and after the reaction is finished, cooling to room temperature. And then, adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 2h at 60 ℃ under stirring to obtain the porphyrin-based metal-organic framework nanospheres with the coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 60 nm.
Example 3
In this example, N-dimethylformamide is used as a solvent to prepare a 10.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and then water is used as a solvent to prepare a 10.0mmol/L solution of copper sulfate. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of copper sulfate solution were added to a 100mL round bottom flask, 10mL of N, N-dimethylformamide was added, 0.05g of benzoic acid was added, and the mixture was stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 130 ℃, the reaction time is 1h, and after the reaction is finished, cooling to room temperature. And then adding 1mL of polyethyleneimine with the concentration of 1mg/L and the molecular weight of 25000g/mol, and condensing for 10 hours at 10 ℃ under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 60 nm.
Example 4
In this example, meso-tetra (4-carboxyphenyl) porphin is first inserted into central metallic iron to obtain meso-tetra (4-carboxyphenyl) porphin, a 1.0mmol/L meso-tetra (4-carboxyphenyl) porphin solution is prepared by using N, N-dimethylformamide as a solvent, and a 10.0mmol/L cobalt nitrate solution is prepared by using water as a solvent. Adding 2mL of meso-tetra (4-carboxyphenyl) iron porphin solution and 1mL of cobalt nitrate solution into a 100mL round bottom flask, adding 10mL of N, N-dimethylformamide, adding 0.02g of benzoic acid, stirring uniformly, carrying out oil bath heating reaction on the uniformly mixed solution under stirring at the temperature of 90 ℃ for 4 hours, and cooling to room temperature after the reaction is finished. And then, adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 2000g/mol, and condensing for 5h at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with the coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 50 nm.
Example 5
In this example, meso-tetra (4-carboxyphenyl) porphin is first inserted into central metal zinc to obtain meso-tetra (4-carboxyphenyl) zinc porphin, a 10.0mmol/L meso-tetra (4-carboxyphenyl) zinc porphin solution is prepared by using N, N-dimethylformamide as a solvent, and a 1.0mmol/L nickel nitrate solution is prepared by using water as a solvent. 2mL of a meso-tetra (4-carboxyphenyl) zinc porphin solution and 1mL of a nickel nitrate solution were added to a 100mL round-bottomed flask, 10mL of N, N-dimethylformamide was added, and 0.02g of benzoic acid was added and stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4h, and after the reaction is finished, cooling to room temperature. And then, adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5h at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with the coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 70 nm.
Example 6
In this example, meso-tetra (4-carboxyphenyl) porphin is first inserted into central metal zinc to obtain meso-tetra (4-carboxyphenyl) zinc porphin, a 1.0mmol/L meso-tetra (4-carboxyphenyl) zinc porphin solution is prepared by using N, N-dimethylformamide as a solvent, and a 10.0mmol/L cupric chloride solution is prepared by using water as a solvent. 2mL of meso-tetra (4-carboxyphenyl) zinc porphin solution and 1mL of copper chloride solution were added to a 100mL round bottom flask, 10mL of N, N-dimethylformamide was added, 0.10g of benzoic acid was added, and the mixture was stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4h, and after the reaction is finished, cooling to room temperature. Then, 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol is added, and the mixture is stirred and condensed at room temperature for 5 hours to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 100 nm.
Example 7
In this example, meso-tetra (4-carboxyphenyl) porphin is inserted into central manganese metal to obtain meso-tetra (4-carboxyphenyl) manganese porphin, a 1.0mmol/L meso-tetra (4-carboxyphenyl) manganese porphin solution is prepared by using N, N-dimethylformamide as a solvent, and a 10.0mmol/L cupric nitrate solution is prepared by using water as a solvent. Adding 2mL of meso-tetra (4-carboxyphenyl) manganin porphin solution and 1mL of copper nitrate solution into a 100mL round bottom flask, adding 10mL of N, N-dimethylformamide, adding 0.05g of benzoic acid, stirring uniformly, carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then, 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol is added, and the mixture is stirred and condensed at room temperature for 5 hours to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 150 nm.
Example 8
In this example, meso-tetra (4-carboxyphenyl) porphin is inserted into central manganese metal to obtain meso-tetra (4-carboxyphenyl) manganese porphin, a 1.0mmol/L meso-tetra (4-carboxyphenyl) manganese porphin solution is prepared by using N, N-dimethylformamide as a solvent, and a 10.0mmol/L cupric chloride solution is prepared by using water as a solvent. 2mL of meso-tetra (4-carboxyphenyl) manganin porphin solution and 1mL of copper chloride solution are added into a 100mL round-bottom flask, 10mL of N, N-dimethylformamide is added, 0.05g of benzoic acid is added, and the mixture is stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4h, and after the reaction is finished, cooling to room temperature. Then, 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol is added, and the mixture is stirred and condensed at room temperature for 5 hours to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 150 nm.
Example 9
In this example, meso-tetra (4-carboxyphenyl) porphin is first inserted into central metallic iron to obtain meso-tetra (4-carboxyphenyl) porphin, a 1.0mmol/L meso-tetra (4-carboxyphenyl) porphin solution is prepared using N, N-dimethylformamide as a solvent, and a 10.0mmol/L cupric nitrate solution is prepared using water as a solvent. Adding 4mL of meso-tetra (4-carboxyphenyl) iron porphin solution and 1mL of copper nitrate solution into a 100mL round bottom flask, adding 10mL of N, N-dimethylformamide, adding 0.15g of benzoic acid, stirring uniformly, carrying out oil bath heating reaction on the uniformly mixed solution under stirring at the temperature of 90 ℃ for 4 hours, and cooling to room temperature after the reaction is finished. Then, 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 1800g/mol is added, and the mixture is stirred and condensed at room temperature for 5 hours to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 200 nm.
Example 10
This example first inserts meso-tetra (4-carboxyphenyl) porphin into the central metallic iron to obtain meso-tetra (4-carboxyphenyl) porphin. Preparing 2.0mmol/L meso-tetra (4-carboxyphenyl) iron porphin solution by using N, N-dimethylformamide as a solvent, and preparing 5.0mmol/L copper nitrate solution by using water as the solvent. 2mL of meso-tetra (4-carboxyphenyl) iron porphin solution and 1mL of copper nitrate solution were added to a 100mL round bottom flask, 10mL of N, N-dimethylformamide was added, 0.02g of benzoic acid was added, and the mixture was stirred uniformly. And carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4h, and after the reaction is finished, cooling to room temperature. And then, adding 1mL of polyethyleneimine with the concentration of 500mg/L and the molecular weight of 600g/mol, and condensing for 5h at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with the coexisting micropores and mesopores, wherein the diameter size of the nanospheres is about 60 nm.
FIG. 1 is a TEM image of micron-sized two-dimensional metal-organic framework-structured nanosheets formed of meso-tetra (4-carboxyphenyl) iron porphine and copper ions, having a size of 1-20 μm and a thickness of 1-20 nm, according to example 10 of the present invention; FIG. 2 is a TEM photograph of porphyrin-based metal-organic framework nanospheres with micropores and mesopores formed by condensing meso-tetra (4-carboxyphenyl) iron porphin with copper ions and polyethyleneimine according to example 10 of the present invention, wherein the nanospheres have uniform particle size distribution and diameter size of about 60 nm; FIG. 3 is a nitrogen adsorption-desorption curve of the porphyrinoid-organic skeleton nanosphere of example 10 of the present invention, which shows approximately type IV Langmuir isotherm and has a specific surface area of about 692.6m2(ii)/g; fig. 4 is a pore size distribution curve of the porphyrin-based metal-organic framework nanosphere in example 10 of the present invention, where micropores and mesopores coexist, the micropores are about 1.2nm, and the mesopores are distributed between 5nm and 30 nm.
In summary, according to the technical solutions of embodiments 1 to 10, the invention utilizes the coordination characteristic of meso-tetra (4-carboxyphenyl) porphine or its metal porphine and copper metal ion under a certain condition, and obtains micrometer-sized two-dimensional metal-organic framework structured nanosheets like thin yarn by adjusting the ratio and heating in an oil bath, and then adds polyethyleneimine to perform controllable condensation, thereby obtaining the porphyrin-based metal-organic framework nanospheres with micropores and mesopores having uniform particle sizes.
In addition, the present inventors have also conducted experiments using other raw materials and conditions, etc. listed in the present specification, in the manner of examples 1 to 10, and also succeeded in obtaining porphyrin-based metal-organic framework nanospheres in which micropores and mesopores having uniform particle sizes coexist.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of porphyrin-based metal-organic framework nanospheres is characterized by comprising the following steps:
reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerant, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure micron sheet;
and adding polyethyleneimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres.
2. The method of claim 1, wherein: the metal porphin comprises any one or combination of more than two of meso-tetra (4-carboxyphenyl) iron porphin, meso-tetra (4-carboxyphenyl) copper porphin, meso-tetra (4-carboxyphenyl) zinc porphin, meso-tetra (4-carboxyphenyl) cobalt porphin and meso-tetra (4-carboxyphenyl) manganese porphin;
and/or the metal ions comprise any one or the combination of more than two of copper ions, cobalt ions and nickel ions, and are preferably copper ions;
and/or the accelerator comprises any one or the combination of more than two of benzoic acid, polyvinylpyrrolidone and biphenyl dicarboxylic acid, and preferably benzoic acid.
3. The method according to claim 1, comprising: dissolving meso-tetra (4-carboxyphenyl) porphin and/or metalloporphin in an organic solvent to form a meso-tetra (4-carboxyphenyl) porphin solution and/or a metalloporphin solution, and mixing with the metal ions, an accelerator, an organic solvent and water to form the mixed reaction system; preferably, the concentration of the meso-tetra (4-carboxyphenyl) porphin solution and/or the metalloporphin solution is 0.1-10.0 mmol/L.
4. The method of claim 2, wherein: the metal ions are derived from a salt solution containing metal ions; preferably, the salt solution comprises any one or a combination of more than two of nitrate, chloride, sulfate, acetate and phosphate; preferably, the concentration of the metal ions in the salt solution containing the metal ions is 0.1-10.0 mmol/L;
and/or the concentration of the benzoic acid is 1.0-30.0 g/L.
5. The method of claim 1, wherein: the molar ratio of the meso-tetra (4-carboxyphenyl) porphin and/or the metal porphin to the metal ions to the promoter is 1:10: 1-10: 1: 10.
6. The method of claim 1, wherein: the organic solvent comprises one or the combination of more than two of N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol and chloroform.
7. The method of claim 1, wherein: the two-dimensional metal-organic framework structure micrometer piece is a gauze-shaped two-dimensional metal-organic framework structure micrometer piece, the size of the micrometer piece is 1-20 micrometers, and the thickness of the micrometer piece is 1-20 nm.
8. The method of claim 1, wherein: the molecular weight of the polyethyleneimine is 600-25000 g/mol; preferably, the polyethyleneimine is derived from a polyethyleneimine solution with the concentration of 1-1000 mg/L.
9. Porphyrin-based metal-organic framework nanospheres having microporous and mesoporous structure prepared by the method of any of claims 1-8, having a diameter of 50 to 200nm, and a specific surface area of 500 to 1500m2/g；
Preferably, the pore size of the microporous structure of the porphyrin-based metal-organic framework nanosphere is 0.8-1.5 nm, and the pore size of the mesoporous structure of the porphyrin-based metal-organic framework nanosphere is 5-40 nm.
10. Use of the porphyrin-based metal-organic framework nanospheres of claim 9 in the fields of gas storage and separation, fuel cell performance switching or biomedical imaging.
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